Insolubilizing and solidifying fatty acid esters of alcohols



atented June 3, 195i Y 'iNsonB'II-,IZVING FAND soLIDIFIG FATT ucm Es'rERs oFALcoHoLs "Serial `N0. 335676 (c1. eetl-21M) bar olvents. and which eii be;1:ea .iiiy pu fied Zeitlimit Geiiiiie suene degree Qf., s wel1i.rie that theZ selig particles stick together inthe form of a Qohererit gel.v

eithatpilefi tette-aalst Qiilyirithe formf visous.,liquidsmrin iizesin- 011 Q1 1 d i to ri an1 .that upon heat'rr 1ef, wither wiihouttheuee Qi Chemicals enigases, alprooess takes place which increases their viscosity i n a Slowly proeressing.;manner: Thus, oi1s which have undergone Suh treatment have been d eseriiedehedied .Qi1. ,b1owi1 oils end the like, their viscosity beine expressed by symbole Y such 215.272; ete. T his i;rreasing deereeof vis,- @Geit has, a1 s9l9een expressed, as. .en indieation 0f Gli girigmoleular ,Weightuehompourids fire geiigeially found, preperedend used in acondt911. wh ere it is ipo ssi b 1e to" dissolve them in solvents b'y the application of heat orumier gie-V cgzripoeiton in an attempt to obtain a stable ,lilies elsebeensumed@empoli Qitinueus llieiiribriponhemial eaimeiiteuch-mmf p's i e ed partiel suit ina cvo waxes, etc., into a state or condition wherein the components thereof no longer stick together after being insolubilized, whereby the insolubilized components can readily be obtained in a substantially odorless and tasteless condition. In this connection, it is still another object to prepare such insoluble products in a form where they may be made water soluble by enzyme activity or by combined enzyme and acid activity, even though such products are insoluble in the usual organic solvents and in water, whereby such products are adapted to be used as an article of food for animals and humans inasmuch as they are digestible in the living body of animals and humans.

Another object is to provide a process which will enable the ready separation of the insolubilized components of the said compounds from the non-insolubilized components whereby to eliminate the latter components which may impart unfavorable taste, odor or other undesirable characteristics to said compositions.

Another object is to provide a physical process whereby the novel compositions forming a part of this invention may be contacted with suitable solvents or swelling liquids in such manner that the various components of the composition do not stick in cohesive fashion, but can be readily separated in either a liquid or solid state without substantial mechanical effort.

A further object is to provide a process for producing the said. solidified and insolubilized compositions forming a part of the present invention, which will be capable of having their color, swelling characteristics, chemical characteristics, and the like, be altered or varied.

Another object is to provide a process whereby oils, fats, waxes and the like which normally exist at room temperatures in more or less solid form or semi-solid form and which normally can be readily melted upon heating and again returned to their original solid or semi-solid state upon cooling, into a non-melting, solid form by use of the present solidication process.

Another object is to provide a process whereby the said fats, oils, waxes and the like,`may be transferred into a novel physical state such that solidilication and insolubilization thereof may be readily controlled to the desired extent by controlling the amount of heat and the length of heating time as well as the intensity of the heat.

Another object is to provide a process whereby the novel solidication method of the present invention may be controlled so as to permit the solidication to take place in a single or a selected plurality of operations which can take place at Widely separated intervals.

Thus, it is an object of the invention to provide a process which will permit an initial, preliminary treatment which will enable a ner uniform solidiiication to occur readily in a desired manner.

Another object is to provide a process whereby oils, fats, waxes, etc., which are partially or completely saturated'and normally known as nondryng or slow-drying oils and the like, may be readily and completely solidified and insolublized.

Another object is to provide a process whereby oils, fats, waxes, etc., may readily be purified or separated into components which are capable of being insolubilized on the one hand, and those components on the other hand which are incapable of being insolubilized.

Another object of the invention is to provide the foregoing novel compositions and products .4 resultant from use and application of the foregoing processes.

With these and other objects in view, which will be understood as the specification proceeds, I have discovered a method of insolubilizing and solidifying fatty acid esters of alcohols which comprises treating said esters with a potentially, free oxygen-yielding compound incapable of forming a metal soap with said esters, at a temperature sufliciently elevated to effect release of said free oxygen in said esters whereby to form a solidified composition which is insoluble in coal tar and petroleum solvents, and which is incapable of being melted without decomposition in the absence of contact with an additional compound, particularly metal soaps of fatty acids.

The compounds and compositions which may be physically altered by virtue of the present process generally include oils, fats, waxes, resins. glycol esters of fatty acids, or partial glycol esters of fatty acids, resinous polyhydric alcohols and the like which, for convenience of the chemist, may be identified as esters or partial esters of fatty acids and mono-hydric alcoholsl di-hydric alcohols and other polyhydric alcohols. Thus, in the case of polyhydric alcohol esters of fatty acids, one or more of the hydroxy groups of the alcohols may be replaced or esteried with a fatty acid radical whereas the remainder of the hydroxy groups may remain unaltered or may be replaced by other radicals. Examples of the latter include alkyd resins which are partial fatty acid esters of polyhydric alcohols wherein at least one of the hydroxy groups has been esteried with a phthalic anhydride radical. Other examples include resinous polyhydric alcohols wherein at least one of the hydroxy groups of the polyhydric alcohols has been replaced by an oxyaryl radical, such as an Oxy-benzene radical or the like.

By further way of example it should be pointed out that the invention is also applicable to partial esters of the type which contain hydroxy groups, such as di-stearin and mono-stearin. In this connection, it is also desired to point out that the present invention is equally applicable to saturated and partially saturated fatty acid radicals as well as to unsaturated fatty acid esters of the hydroxy alcohols, both monohydric and polyhydric.

The particular potentially, free oxygen-yielding catalysts compounds which may be reacted with the said oils, fats, etc., to obtain the solidified and insolubilized compounds and compositions of the present invention may comprise either hydrogen peroxide or organic per compounds of a lipophyllic, oil-soluble character. One requirement of these catalysts is that they be capable of releasing active oxygen in such a free state and in such a manner that the free oxygen is capable of acting as a catalytic agent in promoting the transformation of the initial oils, fats, waxes, etc., into a solid, insoluble, non-melting state. A further requirement of the organic, potentially oxygen-yielding peroxide catalysts is that they be oil-soluble or lipophyllic in character; that is, that they have a greater affinity for lipids generally than they do for water, and as such they must be capable of being uniformily distributed in the initial starting compounds which are thereby solidied and insolubilized. Perhaps the most important requirement of the potentially, freeoxygen-yielding catalyst compounds is that they be incapable of forming a metal soap. By metal soap I mean to include any metal compound S of .-an organic acidor :ester thereof ywhich is at leastpartially soluble in a vfatty acid esterof an alcohol.

It is surprisingindeed that hydrogen peroxide may be successfully vused in the practice of the invention in View of its hydrophyllic character, but I have found that by maintaining the reaction temperature near, at or above the boiling point of the hydrogen peroxide, I am able to effect the transformation by repeating the action one or more times. I have also found that continual Astirring of the reacting mass contributes appreciably to the transformation reaction. While I do not desire to be restricted to any particular theory, it is my observation that this water of the H2O2 boils off during the transformation before it can hinder the `catalytic action of the free, active oxygen.

The organic, potentially oxygen-yielding catae lyst compounds are generally of the alkyl, aryl, and alkyl aryl peroxide type which are of an oil-soluble or lipophyllic character. Thus, I have selected certain specific catalysts which are representative of the class of catalyst compounds which come within the purview of my invention. These include Diacetyl peroxide,

Tertiary butyl perbenzoate,

Di-tertiary butyl peroxide,

Tertiary butyl hydroperoxide,

Benzoyl peroxide, and

Dimethyl benzyl hydroperoxide (curnene hydroperoxide).

Likewise, oxygen-yielding, organic 'per coinpounds which are more lipophyllic than hydrophyllic in character are operable; Whereas; cornpounds which are both hydrophyllic and lipophyllic in a state of balance are generally operable under more extreme conditions of heat, excess amountof catalyst, time of reaction and repetitions of the present process. Moreover, I have found that ordinary metallic peroxdes, such as magnesium peroxide are not operable because they result in the formation of a metallic soap which, according to my discoveries as set forth in my copending application, Ser. No. 748,665, now Patent 2,476,879, issued July 19, 1949, causes the solubilization and liquefaction of the compounds treated.

Moreover, I have found that the efficiency of the transformation and the uniformity of the product can be increased by adding to either the initial compound or the catalyst or both, an additional compound Which is a solvent for either the initial'compound and/or the catalyst. Thus, I have found it advantageous to add one part toluene to two parts tertiary butyl per-benzoate catalyst. By way of further example, '7 parts dimethyl phthalate may be added to three parts di-acetyl peroxide. In this connection, it has been found desirable to select a catalyst of the above'type, the boiling point of which is in the neighborhood of the reaction temperature at which the catalyst is especially effective in releasing the free oxygen, whereby the presence of the added solvent serves 'to intensify the solidification.

The solidication which takes place actually produces a solid state in contrast to the known state of gelatinization. The invention 'is as equally applicable to natural or synthetically produced non-gelatinized compositions as it is toA partially and completely 1 gelatinized f compositions. Howeven' in thelatter lcase, I- have found .6 by V.actual .experimentsthat a.. higher`r percentage of insoluble matter .is produced although: it appearsftoib'e. developedlwithin andfclosely adjacent toxthev` gelatinuous portions. Thus', I-have-found that the separation oflth'e.-insolubilized,.solidified portion from .the nonf-.soli'diii'ed portion-of the partially or completely gelatinous "mass is rendered more ,difcult Accordingly, If :have found `that it requires repeated andiextend'ed separation steps to. achievezanactual' y-ieldfrwhi'chis 'equal vto the percentage'of solidicationiithat has takenfplace'within'the gelatinous mass.

The following working examples Will Iservetoillustrate the processes and products 'comin'g' within the realm of the present invention and will also serve to illustrate the use of a representative number of the class of initiaLstarting compounds and compositions.. potentially, free oxygen-yielding catalysts, solvents, and solidified and insolubilized products covered by the present invention:

Example 1 About 500 parts linseed oil were mixed with 25 parts toluene solvent and 50 parts t-butyl-.per-

benzoate catalyst and slowly heated. *When'the first gas-bubblesbegan to develop atthe'bottom of the container, the heating was continued under stirring. When the temperature reached about C., the heat source Wasshutoff'and stirring was continued. The temperature-continued to rise during the gas development. When it had reached about C., the mass solidified to a fluffy substance 'which was raising in'the kettle. The temperature continued rising until the reaction had come to an end at which time the reaction product had-solidified. The product also may be obtained without the 4additiorrof -solvent and without stirring of the mixture during the transformation.

It has been found helpful in observing :the course of the reaction,.to drop asmall samplev of the compound on a hot placeto indicate the for mation of the non-melting, solid product. After solidication, further heat development .can lbe broken up by stirring `cold air into the solidified substance or by transferring the solid substance into a cold, neutralliquid. AThe product .of this process isin form of a solid, fluffy or poppy vsub stance which will not melt Without decomposition. It does not dissolve in toluene, benzoyl,

petroleum naphtha or any of the usual solvents,

tures around and-above 50 C. yItcanalsozbe boiled in water and then dried in an oven,.or..

it can be dried at roomitemperature overdesic.- cator substances. purified by boiling in water and then treating with organic solvents. These purication treatments Acan be repeated until the desired state of isolation of the insoluble product and the* desired conditions of taste -and odor `have been reached.

In heating 'the solid substance in an oven-:at

about 55" C. for an extended period, 'or `at about 100' .C -for a shorter L period, Va lfcertain'fmodl'ica- The product can.

The product can likewisefbe.

tio'ri can be obtained, whereby the solidified product darkens or appears more intense in color. It has been observed that such modification substantially ceases at a certain point and thereafter further heating for 48 hours at 100 C. does not appreciably modify the product.

While preferred heating temperatures for the various stages of treatment of purification and drying are set forth in the examples, it will be understood that temperatures will vary in accordance with the physical and chemical condition of the starting materials, the quantities of the starting materials and other substances employed, and the form and the speed of heating.

Example 2 The process set forth in Example l was prac-v ticed with the following materials:

Added Volatile Solvent Oil Used Source of Free Oxygen 1010 parts China wood 8 parts t-butyl perbenzoate.

4 parts d-tertiary-butylperoxide.

mixture oi 9 parts tbutylperbenzoate with 4.5 parts t-butyl-hydro-pero1. 51x31 parts Florida tung o 120 parts soybean oil with parts rosin.

20 parts linseed oil (break stabilized) with 10 parts tung oil.

80 parts perilla oil with parts China Wood 011. (j) 26 parts linseed oil Z-2 ox c. (d) 3 parts t-butyl perbenzoate.

(e) l0 parts t-butyl-perbenzoate.

2.3 parts 95 benzoy! peroxide Wth stearic scid.

Example 3 The process set forth in Example 1 was followed in solidifying cottonseed oil, an oil of the group of semi-drying or non-drying oils. 44 parts cottonseed oil were mixed with 2 parts toluene and 4.8 parts t-butyl-perbenzoate and heated as set forth in Example l. Gas development occurred especially between 150 and 200 C. After the reaction had quieted down, the oil had become more viscous than it was before the treatment, but it had not yet been solidified.

' The ultraviolet spectrum of the oil in this modi fied condition showed a clear shifting in optical density. The modified oil also had a higher viscosity and lower iodine number than the initial oil.

After repeating the reaction on the modified oil with an additional 3 parts of the same catalyst, solidification was obtained at about 140 C. in the same manner as the drying oils of Examples 1 and 2. The solidified sustance was purified by immersing it into petroleum ether for 15 minutes, decanting the ether, and repeating the extraetion. After filtering, the solid substance was pressed against a porous filter paper, washed again with petroleum ether and dried. Then it was further purified by heating it with water and again dried. A loose and light colored solid substance was obtained with a very slight degree of odor or taste which can be removed by further extraction.

Example 4 The process set forth in Example 1 was followed in solidifying cottonseed oil. The oil was first treated by distilling off the oily substance. In this particular example, 19% of the substance of the oil was removed by vacuum distillation and a clear oil was obtained. The clear oil was treated as set forth in Example 1, by mixing 44 parts of' CTI the modified cottonseed oil product with 2 parts petroleum naphtha and 2.5 parts t-butyl-perbenzoate. In heating it as set forth in Example l, the substance was solidified in one treatment between, about and above 135 and 200 C.

Example 5 The process of Example 1 was applied to corn oil, another semi-drying or non-drying oil, by treating it in the two steps as set forth in Example 3. 56 parts corn oil were treated initially with 5 parts, secondly with 3 parts t-butyl-perbenzoate, whereby solidiiication was obtained.

Example 6 This exemplifies the solidiiication of a senildrying or non-drying oil together with a drying oil, whereby the solidication occurs more rapidly. 45 parts corn oil were mixed with 10 parts tung oil and 7 parts t-butyl-perbenzoate. They were heated in accordance with Example 1. Solidification occurred in the initial treatment between at about 135 to 175 C.

Example 7 The process set forth in Example 1 was applied to a plant Wax; namely, carnauba wax. 58 parts commercial carnauba wax were melted by heating to about C. Seven parts t-butyl-perbenzoate were added as a source of free oxygen and the heating was continued. At about C., gas development occurred and the temperature continued to rise, even after removal of the reaction vessel from the source. Solidification occurred freely at about C. The solid product did not melt on a hot plate. It was purified by boiling it in about 4 times its own weight of toluene followed by hot filtering. The operation was repeated with toluene, again with petroleum ether, and after drying, again with ethyl alcohol, and finally boiled twice in Water to remove all traces of decomposition products resulting from the catalyst treatment. A yield of about 45% insoluble product substance was obtained.

Example 8 Plant waxes generally require more than one treatment with the oxygen-yielding catalyst to achieve solidification, as shown by the following:

Number of Treatments Wax Used Source of free oxygen (a) 25 grams Ouricuri wax (h) a pLmt wax derived from herbs or shrubs 25 g. Candelilla wax (c) a plant wax derived from fruits and berries; 26 g. Japan wax Example 9 In this example cod liver oil was used in producing a solid oil substance according to the process set forth in Example, 11. 40 parts cod liver oilwere mixed with 1.5 parts benzoyl peroxideand heated under stirrngat'about 85 C. The solid source.of"'oxygen appeared to go into a liquid combination with the oil, andv on continuing the heating, the free oxygen Was developed. The heatingwas continued to about 200 C. Theclear modifledoil was storedifor severalivveeks and on heating it again with 2:5 parts t-butyl-perbenzoate. solidication occurred. As set forth in Example 4, the oil can be initially distilled to remove aportion of the nonsolidable components.

The same process Avvas carried out with llard oil, solidiflcation being obtained inthe same manner.

Eample 10 The process set forth in Example 1 Was applied to a fish oil; namely, Menhaden sh oil. 40 parts of the oil Were solidified in two steps with the same souroeof freeoxygen, using` a mixture of the oil with 2 parts xylene and 4 parts t-butylperbenzoate and heating it to about 200 C. After cooling the product to about 85 C., the substance was again treated with 3 parts of the same catalyst.

The oil was characterized after the rst treatmentuby a change in viscosity, a decrease in the iodine number and a shift in the optical density in its ultraviolet absorption spectrum, in comparison to the same figures for the initial, un-

treated oil.

Example 11 The process set forth in Example lwas applied to bacon fat, a xed oil which has a solid appearance, at normal room temperatures. 30 grams commercial bacon were slowly heated so that the fat substance became liquied and could be separated from the non-fat substance. In this liquid form, the oil-like fat substance was decantedA and, after cooling, a white fat was obtained. 20 grams of this white fat were mixed with 2 parts di-tertiary-butyl-di-perphthalate. One part toluene was added and the mixture heated to about 180 C. After cooling to about 70C., the substance was heated with about 1.8 parts t--butyl-perbenzoate catalyst. Solidication occurred and the productl Was then purified .by extracting-the substance ina Soxleth extraction apparatususing a petroleumderived solvent as the purifying liquid. The purified substance consisted offloose, light solidv particles of a slightly creamcolored appearance;

Example 12 The proessetforth .iuExample 1 Wasarplied to beeswax, Aan insect Wax. 41 parts of commercial whitebeeswax were melted and mixed with 5 parts of t-.butyl-perbenzoate. Gas development occurred vehemently on heating between 140 and 164 C., which continued after vessel was removed from the-hot plate. No solidication having occurred heating was continued up .-toaboilt 200/C. Thenthe-massgwas ,allowed itocool to about 90? C. Again 4pagrts of the Sarnesource of` freeoxygen wasfadded .and theheating procedure was repeated. ySince.solidication had'not yet occurred, a third treatment with 4 parts of the same perbenzoatewas carried out which resulted in solidicationat about 170 C. The solid product Was purified byex-traction-With toluene-and, after drying, byboiling-inwater and drying -at 115 C. for 5 hours. A yield-cf-'about'50% insoluble product wasobtained.

Exemple 1,3

Type of Wax 25 g. shellac Wax, anv insect wax.

25 grams spermacetti wax.

32 parte Floriday Tung oil and 8 parts Candelilla Wax.

3 g. t-butyl-perbenzoate was utilized in each of three treatments. Solidflcation occurred` at around 165` C. About 72.4% ,yieldvofsolidied substance .was obtained after purication.

V4 g. t-butyl-perbenzoate developedzaivery stormy reaction with strongy heat vvdevelopment. Partial solidification occurred in the first'treatment: After cooling, ,3 g. of the same `catalyst was added, followed by heating. Whenthe reactionbegan', the vessel Wasiremoyed from the heater and the temperature continued rising to above 205Q C; The weight of the solid jnal productivas not muchdiflerent from the weight ,ofthe initial woolfat.

Treated with 4 grams of tbutylperben zoate. T he composition washeatednp to about-190C. After cooling;llygrams of the same catalyst -were addedvwhich resulted in a violent reaction and the formation of a yellowish oilysubstance. After Acoolingfto about "G 2.- 5\g.of the same catalyst was added. The composition `was then heatedto yabout C.,`after-which the temperature rose steadilyto about 200 C. and the lfresilting product became fully solidi- The mixture was treated withAparts 95% benzoyl peroxide in stearicacid. The mixture was Yheated to above 200 C. and then cooled. Thereateryvg. of the same catalyst were added,r tliereaction beginning at .about 210 .0.at which time the mass turned to a browish solid. f

Example 14 4From the full purication inv solvents and in Water, about 28 to 30% solid insoluble, -infusible substancewasisolated `at that point of vthe reaction;

Example 15v Oxygen-yielding Volatile-SOL- Synthetm Q11 catalyst vent added (a.) 92 parts isomerized Y8 .parts diacetyl per- 16 parts dilnseed oil (commeroxide. m e t h y l cial Isoline Z3). phthalate.

(b) partssynthetic oil, 1.8 parts benzoyl perobtained from comoxide. bining. sorbitol vwith soya fatty acids (commercial Atlas 87er). I

(c) 40 parts ofa synthetic 4 parts di-tertiary-ouoil from sorbitol and tyl-diperphthalate linseed fatty acids (a solid that meltsin (commercial Atlas the oil at about 75"l G 875). C. I

(d) 33 parts of a linseed 1.5 parts di-tertiaryoil which Was reacted butyl-diperphthal with maleic anhyate. drate (commercial Trimol").

(e) 42.5 parts dehydrated 4 parts'di-tertiary-bu- 2 parts-petrol castor oil (commertyl-diperphthalate. naphtha; cial) Castung 403- (f) 40 parts dehydrated 2 di-tertiary-butylcastor oil (commerperoxide. Solidicial Castung 403` cation begins at Z3"). 0.., but temperature goes up to C.

(g) 30 parts synthetic tri- 3 parts t-butyl-per- 2 parts petrolglyceride oil (cornbenzoate. naphtha. mercial Neo TM200). v

`(b) 48 parts of the same In all above instances, solidiflcation was achieved in accordance to the process set forth in Example 1.

Example 16 This exemplifies the process of Example 1 as applied to a synthetic wax-like material solidified according to Example 1.

(a) 22 g. polyethylene glycol di-tri-ricinoleate were heated with 2 grains t-butyl-perbenzoate. In the Yfirst treatment a strong reaction occurred and solidification was reached between 150 and 170 C. The purification was performed in the same manner as hereinbefore set forth.

(b) The solidification of another product of a dihydric-stearate, an emulsiiiable wax-like esterification product of a dihydric alcohol (like diethylenglycol) with a fatty acid, obtained under pressure and heat in the presence of a catalyst, e. g., sodium glycerophosphate, was successfully accomplished. In heating 30 parts of this ester with 3 parts t-butyl-perbenzoate up to 210 C.. and a second time with the same amount of the reagent up to 200 C., no solidication occurred. After a third treatment with 2 parts of the reagent soine solidication was produced above 150 C. and after a fourth treatment with about 2 parts of the catalyst rapid solidification of the ester resulted.

(c) In a similar way full effect was reached at the fourth treatment of 42 parts diethylene glycol monolaureate (Glaurin) with 4, 3, 3 and 2 parts of the t-butyl-perbenzoate respectively. Solidification occurred around 160 C. and the temperature rose to about 190 C. Purification was performed with the usual solvent treatment.

Example 1 7 This exemplifies the application of the process set forth in Example 1 to such compounds which contain groups of polyhydroxyl alcohols and fatty acids with phthalic anhydride (commercial "alkyd resins) In this example the alkyd resin is used in a form wherein it has been modified with a drying oil. 150 parts of an alkyd resin of a long oilmodified group, obtained from polyhydroxyl alcohol and phthalic anhydride and soybean oil substance were mixed with parts toluene and 14 parts t-butyl-perbenzoate and treated as set forth in Example 1 until solidification occurred. Solidilcation occurred quite rapidly.

Eample 18 This exemplified the application of the process of Example 10 to another group of alkyd resins which contain non-drying-oil substance instead of the drying oil substance of Example 10.

(The product obtained was well solidied, but still less uniform in character than the following examples.)

Treated initially with 3 5parts tolparts benzoyl peroxide uene. and, after cooling, with 3 pirts t-butyl-perbenzoa e.

alkyd resin.

(c) 16.5 parts ol the same Two successive treat- 11 parts xynldyd resin. ments with 1.5 parts tlelie.

butyl-perbenzoate.

12 Example 19 The following embodiments exemplify modification of the rate of solidiflcation in accordance with the processes as set forth above, such modification being accomplished by combining slower solidifying compounds with those which react more rapidly, or by modifying those which are solidified rapidly by combining them with others which react more slowly.

. Volatile Compounds for Modifying Catalyst Oxygen Solidi'cation Substance Source Sl'it (a) 15.5 parts alkyd None 1.5 parts t-butyl- 5 parts resin with so bean oil perbenzoate. toluene. substance commercial Aroplaz 1085).

(solidified in two steps around to 180o C.)

(d) l5 parts oi the same alkyd with non-drying oil.

3 parts Cli na wood oil.

1.8 parts l (solidified in one step below C.)

Example 20 This example shows that the solidification products can be effected by enzymes and acids in the process of digestion.

In the course of the specification it has been pointed out that the insolubilized solidifications of these esters are insoluble in the usual solvents and in water. Thus, these stable and easily transportable materials can be used where, for instance, ordinary oils would be used, so long as it is not necessary to use such oils in liquid or soluble form. To demonstrate this, the present example shows that the insolubility of the solidified substance does not eliminate its digestibility and it shows that the solidified substances of the present invention are not basically different in this respect:

(A) Tests were made by actual feeding of the solidified substances to a living animal, a young White male rat of known background and of an initial weight of 219.3 grams. The feeding circle was begun after a 24 hours period of starving the animal with water supply exclusively. Each day afterwards, the animal received a food offering consisting of 2.5 g. dry solidified ester of changing origin made in accordance with the present invention and a mixture of 13 g. of the same solidiiication mixed with 20 g. scrambled raw egg substance. 'Ihe weight of the intake and the content of insoluble substance in the excrements was checked in each case and the percentage of digested solids was calculated. The animal was {edionrsubsequent daysfswitlr-.solidificationsot the following examples:

() `1Vlixtureof8-partssolids of"Example'11: animalfat (bacon fat). with parts lsolids of Example- 9.: animal oilv (codgliver oil) y (1c)-4 ExamplelZ: Waxfromanimal'source (beeswax) (d) 'Example' 15: Synthetic triglyceride oil (Neo Fatv290) (o) ,Example 5: Vegetable.non-dryinggroil (cornoil)A Example-7: Plant-wax-(carnauba wax) (y) Example 18: Oil-modified alkyd resin (Rezyl 'Inall cases `the animal took; in dailybetween 10 and-gg.' of"\thesolidifcation. 'In determining the amount of insoluble` matter-remaining in .the excrements, the fact was neglected that even under, normal kernel feeding nditions, the animalsexcrements,'containabout.45% insoluble substancia Butw even 'oyerlooking Athis fact, and' deducting all" insoluble' substance inthe excrements 'from theseftestsfas Aundigested solidications, the v.folivlowingresuli-,s Were-obtained:

V.lla/eragewofdigested substance-from;test ato e (between/5.3% and 74% fonthe various vsano-.- ples).

This-giveslan='average-off54.5% forallitests which is-` not=-mueh different from the' normal data `on the usual food ofthesameanimal. After'testg, ftheweightoftheanimal'was--Zl5:21g.

(B)- Ina seoondlseries lthe vsolidigcationsrwere first soaked in water for 2li/hoursbefore feeding andZ g. bread -Wasadded tothe-daily dietfor amore complete'nourishment; the-results-were as follows:

(h) Solids of Example 1 :(i) Solids-.of Example `lll' (le) Solids `ofE'xample 12 Based on' 5 days"feeding. the.. percentv of. di.- gestedsolidstwent upto 56:5.to 80.3% with... an average-ofa"67.'3% and the weight ofn the animal rose'to12285 g.

(C) At-the 'end of the test series, mixtures of thesewater-soaked solidif'cati'onsy (1'. .part dry weight)V with" theV normal kernel. food` (3 parts) were given; readily -accepted and consumed.

The testsl show that the solidications. are indeed` digestible'. The vabovesolidications` were also eatenl inA small amounts by several humans and were-digested in the normal manner; so far las isknown, withoutilleiects;

Example 21 This rexempliiies the application `o'the-V present .processi for thesolidication: and linsolubilization of coatings, impregnations and.' other. forms of layers producedfrom compounds containing poly- -hydroxylralcohol-fatty-acid esters; including such compounds `which contain other" esterE forming groups; that is, including; '.forxinstance; alkyds, being'applied 'forz'ftheg purposeaof Tilmjorming in a condition ywhere they vare combinedwith atleast one thinning liquid.

:llfpartssof Vbodied linseedoil (Z.-'2)fwerenixed with .25partstoluene. To this,- mixture, `5::pfart`s Itertiary butyl hydroperoxide in an Aoil-solvent mixture .were added.`

In; another embodiment '5 parts tertiarybutyl perbenzoate were added .directly- :tot :the oil; and

warmedslowly' -togetherfata temperatureeffbelow yulolemixturebeingsdilutedwitlrscrlverlt.

Thesegmixtures. were storedforrseverak months 5 `withoutanysubstantialinuence'on.therstaloility Vofthe mixture. However, upon .heating the mixetures toV a temperaturepermitting; the: release fof oxygen and, the- `partial escape off. solvent, the solidication occurred as Seifferth inExamplerl.

When. parts fof the mixturev were; spreadA` over a--base,A as by coating-:on a: panel,.or bydipping apiece of metal in ythe mixture, an insolubilizaltionrwasproduced when 'such' coveredxparts were .exposed ina heated drying oven, or; uponsexpozsure to infra red light, or otherwise heatedso that the free oxygen wasreleased from the coating mixture. after. ts. application. It was found that the film had a 'higher percentage ofi'nsoluble 'substance' than a similar iilrnproduced` from the same initial oil and underv the same conditions without utilizingrthe.present-catalysts (using similarnlm thickness, during temperaturejdrya ing'time; etc.)

Thezsame process :was also successfully ap.- pliedsto the remaining natural 'and vsynthetic Yini#- 'tialcompounds' cited in the .preceding examples.

Example `2.2

The oxygen-yielding substance itself: may-be used asta solvent for the compound which is'to beapplied and subsequently solidified. In yaccordance with this discovery, rparts-of` soya'.- bean oil werefmixed' with 6 partsY butylehydroperoxide 'and vtreated* like the coating compounds set forth'in xample 21.

Example. 23

Exemplies theapplication of the process as setforth in` Example 21 to mixtures of fixed voil andy alkyd compoundswith other substances:

`A mixture of V25 parts alkyd resin (modified with soybean oil substance) withA 10 parts mel'- amine type resin (melamac resin) and r15v parts synthetic-oil (derivedfrom sorbitol with linseed fatty acids) was mixed with 18.5 parts toluene. 25 parts mineral spirit and 6.5'parts offbutanol as-solvents. To parts thereof, 5 parts t-butyl hydroperoxide werel added' and the product was treated as set forth in Example 21 as a coating composition. Steel panels were dipped into the solution, allowed to drain and were exposedto a dryingoven "C.) A'well solidified and wide'- ly insolubilized film was obtained.

Emampze 2.5

Exempliesthe application of 'the process as'fset forth in Example 13 to a coating` composition which contains pigments in addition to `the sol'- Vulole ingredients:

(af)- Acomposition wasA obtained=by mix-ingrand -mi1ling;together. 140i) parts lead chromate,- 68D parts redlead and-.320 parts zincox-i-de with18;00 -paritsizbodied .linseedoil (Z1-:2) andloparts-of petroleum.naphtha; solvent; :.'Ilheneeopaaztszfof this paste were mixed with 300 parts of a 50% solution of soyabean oil-modified alkyd resin, 120 parts of 50% solution ofa melamine type (melamao) resin and 325 parts toluene as thinner. To this composition, 5% t-butyl-hydroperoxide was added. This product was then used as a paint. It was applied as a coating and dried at about 130 C. A well-cured solvent resistant solidied coating wasI obtained.

(b) 89 parts commercial, standard Army olivedrab paint was thinned with 8.9 parts toluene and 2.22 parts t-butyl perbenzoate and the product was treated as in (a) above; a highly solidified, solvent resistant coating of high quality was obtained.

Example 26 This exemplifies the application of the present solidication process to a coating composition which contains at least a portion of fatty acid 'esters of polyhydroxyl alcohols, after such comlposition has been applied to another material.

100 feet of ber glass covered electric wire were coated with a coating composition containing 50 parts of a commercial varnish produced at least partially from fatty acid esters of polyhydroxyl alcohols (in this example the varnish was based on a linseed oil composition dissolved in 50 parts mineral spirits) The wire was allowed t drain after being immersed in the varnish, and passed through an oven heated to 110 C. in 5 minute stages. The coating composition began to set, but had not been fully cured. Before curing had been completed, the wire was passed through a container holding a mixture of 10 parts tertiary butyl hydroperoxide in 30 parts petroleum naphtha. Alternatively, the liquid catalyst can be applied by dipping, spraying or the like. The coated catalyst treated wire was passed in minute stages through an oven heated to 120 C., resulting in a well-cured, highly insolubilized coating.

Example 2 7 The catalyst, cumene hydroperoxide is a commercial product containing about 68.1% dimethyl-benzyl-hydroperoxide in dimethyl-benzyl alcohol and acetophenone, the actual hydroperoxide having a calculated active oxygen content of about 45 parts linseed oil were mixed with 5 parts commercial cumene hydroperoxide and 3 parts toluene. On heating, a vehement reaction occurred and the temperature went up to about 190 C. No solidication had occurred. The substance was allowed to cool to about 120 C. and 2 parts -catalyst were added. On heating, Isolidiilcation occurred rapidly. After boiling the reaction product in toluene, filtering and drying the solid substance, 38 g. or (89%) of the initial oil were obtained as a solidification.

Example 28 The solidication of fatty acid esters of resinous polyhydroxyl alcohols may also be accomplished by practice of the present invention as shown by the following example:

123 g. of a synthetic resinous polyhydroxyl a1- cohol, the condensation product of bis-phenol and epichlorohydrin (commercial Epon resin, in particular type No. 1004) were esteried by heating with 82.8 g. fatty acids. In this case, the chemically conjugated linseed fatty acids (commercial Conjulin fatty acids) were used. The esterication was obtained in the usual manner by heat-.- ing the compounds in an oil bath under continuous stirring and passing a flow of carbon dioxide through the reaction vessel. Reaction was observed around 190" C. and the heating was continued to around 230 C. The resulting ester was a resin of a wax-like, milky appearance melting around 70 C.

To produce the solidication products in accordance with the present invention, 42 parts of the ester were melted with 6 parts toluene and 4 parts of t-butyl-perbenzoate catalyst. Three catalytic heating treatments were made, whereby solidication was obtained. The reaction product was puried Iby boiling twice in toluene, filtering and drying. 34 g. dry solidication were obtained. A

Eample 29 To exemplify the effect of the free oxygen action as procured from a substance which is capable of releasing such active oxygen, but which is not soluble in oil, hydrogen peroxide was used as follows:

(a) 47 g. bodied linseed oil were mixed with 15 grams 30% hydrogen peroxide and heated under stirring. Heavy foaming developed around C. from the evaporation of the water and the oxygen release. Heating was continued up to 210 C. without solidication. After cooling to around C., 10 g. hydrogen peroxide were added followed by heating up to 210 C. No solidication was obtained and after a third treatment with 9 g. hydrogen peroxide, solidication occurred. The solid particles were somewhat softer in texture than the other examples and swelled to a greater extent. They also exhibited a greater cohesive tendency than the solidifications from the previous examples. After heating twice with toluene, filtering and drying, 24 g. dry solids were obtained.

(b) '75 g. bodied linseed oil were heated in a vessel equipped with a mechanical stirrer. When the temperature reached about 90 C., the 30% hydrogen peroxide catalyst was allowed to drop continuously into the mixture. The rst run was made with 25 g. peroxide. The water appeared to evaporate rapidly and gas development appeared to effect the oil under stirring. After the peroxide had been added, the temperature was allowed to raise and the reaction died down. Heating was discontinued at about 200 C. A slight gel was obtained. After resuming the heating of the mixture which had cooled off to about 95 C., peroxide was allowed to drop into the mixture under stirring. When about 15 g. peroxide had dropped in and the temperature had increased to about C., solidication occurred to such an extent that movement of the mechanical stirrer was halted by the substance. The product was similar to that obtained in (a) above.

The present invention can be used for the production of the insolubilized form of fatty acid esters of polyhydroxyl alcohols and combinations of such esters with other ester-forming acids and compositions of such materials with other substances. Such products can be used as a stable, easily transportable and substantially resistant form of oil, wax, or fat products so long as it is not necessary to use these substances in liquid or soluble form.

The products of the present invention can also be separated from admixtures of the initial ester substances which do not take part in the actual solidication and which may be undesirable because of taste, odor or other undesirable qualities.

The solidied substances of the present in# vention can be solubilized as set forth in my (zo-pending application Ser. No. 748,665 and can be` used in the production of coatings, plastic compounds, etc. In this form ofv use, the present invention makes it possible to separate the part ofthe substance which is actually capable of solidification from other` substances` which 'are not capable of solidification, and combine such isolated products with other materials which are selected because of their characteristics, or to produce compounds Which are more uniform than in their initial forms and which are therefore compatible With substances which are not compatible with the initial substance;v

By applying this invention to solutions, it has become possible to produce coatings, impregnations, and similar compoundsV which can be stored, shipped and applied to the desired base in the desired form and which can then be insolubilized to a high degreeY of insolubilization.

By virtue of their easy form of handling, the catalysts. themselves, or mixtures of the catalysts with other materials, can be kept separatelyand can be added to such compounds as intensiiiers ofthe insolubilization at any time before ordering'the actual application of the solution. They can also be used on previously applied and partially driedcoatings, for further intensifying'the insolub-ilization of the film, as by immersing the applied coating in the catalyst or to its combinations, and exposingsuch coated and immersed parts to conditions Where the oxygen is freed directly on the coatings which are further to be solidified. Such immersion may be effected by dipping, spraying, etc. The coated substance, for instance long piece goods, like fabrics, cables, paper, etc. may be contacted by the' free oxygen-yielding catalyst in a continuous process before completing the insolubilization of the coatedv materials. A` further aspect oi' my invention is that the processes andl products disclosed and claimed hereby are adapted to be used in conjunction and cooperation With the processes and products disclosed and claimed in my copending application Ser. No. 748,665, now Patent 2,47 6,879, issued July 19, 1949. Briefly, this latter application relates to a process for solubilizing and liquifying fatty acid esters of alcohols, such as fixed oils, which are in a highly gelatinized state, by mixing them at elevated temperatures with a metal soap.

To avoid needless repetition in the present specification, I desire to state at this point that I have solubilized :and liquified all the insolubilized, solidified products made in accordance with the foregoing Working examples by utilizing the process of my aforesaid copending application. It is my intention that the aforesaid copending application be a part and parcel of the present specification to that extent and therefore my present application is a continuation-inpart of the aforesaid copending application Ser. No. 748,665, now Patent 2,476,879, issued July 19, 1949, in this respect.

In fact, the only process presently known to me for solubilizing and liquifying the solidified and insolubilized products of the present invention without decomposition is by use of my discovery as set forth in my aforesaid copending application.

It will be apparent that in this respect, my discoveries enable a complete and continuing cycle of physical transformations from a liquid, soluble state to a solidified, insoluble state and back again, regardless of Whether or not the materials treated at any stage of the transformation are in aV nQn-gelatinized, partially-gelatinized or highly gelatinized form.

In the foregoing specification and Working examples, I have selected a representative number of the many initial starting materials andoxygen-yielding catalysts which may be utilized with the process of my invention in order to obtain the novel resulting products. Among these c ornpounds, all of which IV intend to include'V Within the scope of my appended claims, are the following;

Fatty acid esters of alcohols From vegetable sources Drying Oils Semi-drying anclnon-drying oils Waxes and Wax-like niatcrialsv From animal sources Animal oils Animal fats Y Waxes and Wax-like substances Frommineral sour-ces Montan Wax Syntheticoils and wax-like substances Oil-modified alkyd resins c Fatty acidsl esters of resinous polyhydroxyl alcohols rIfherefore, it Will'be apparent that-by use of the term ffattyacid estersof alcohols, I mean to'include both natural and synthetically produced compounds;` In addition, I mean to include, monohydroxyl; dihydroxyll andl other polyhydroxyl' alcohols' including resins'an'd resinous polyhydr'oxyl-alcchols. Byuse ofthe term 0ils,- Ij'mean vto include both natural and synthetic-oils and ,fats'and other lipids.

However, it will be apparent and understood that variousl modifications andv equivalents coming' within the realm of my discoveries-may be used andv I intend to include thesewithin the scopeof the appended claims defining my invention. f

I'claim: f

1. A method of insolubilizing and solidifying higher l:fatty acid esters of alcohols characterized by their solubility in coal tar and petroleum solvents, Which comprises treating said esters with at least about 4.5 percent by weight of an organic peroxide, at a temperature of at least about C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles, said reaction product being insoluble in coal tar and petroleum solvents.

2. A method of insolubilizing and solidifying higher fatty acid esters of alcohols characterized by their solubility in coal tar and petroleum solvents, Which comprises treating said esters with at least about 4.5 percent by weight of an alkyl peroxide, at a temperature of at least about 90 C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles, said reaction product being insoluble in coal tar and petroleum solvents.

3. A method of insolubilizing and solidfying higher fatty acid esters of alcohols characterized by their solubility in coal tar and petroleum solvents, Which comprises treating said esters with at least about 4.5 percent by weight of an aryl peroxide, at a temperature of at least about 90 19 C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles, said reaction product being insoluble in coal tar and petroleum solvents.

4. A method of insolubilizing and solidifying higher fatty acid esters of alcohols characterized by their solubility in coal tar and petroleum solvents, which comprises treating said esters with at least about 4.5 percent by weight of an alkylaryl peroxde, at a temperature of at least about 90 C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles. said reaction product being insoluble in coal tar and petroleum solvents.

5. The method set forth in claim 2 wherein the alkyl peroxide is an acetyl peroxide.

6. The method set forth in claim 2 wherein the alkyl peroxide is a butyl peroxide.

7. The method set forth in claim 3 wherein the aryl peroxide is a perbenzoate.

8. 'I'he method set forth in claim 3 wherein thearyl peroxide i-s a perphthalate.

9. The method set forth in claim 4 wherein the alkyl-aryl peroxide is a methylated benzoate.

10. A method of insolubilizing and solidifying higher fatty acid esters of monohydric alcohols characterized by their solubility in coal tar and petroleum solvents, which comprises treating said esters with at least about 4.5 percent by weight of an organic peroxide at a temperature of at least about 90 C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles, said reaction product being insoluble in coal tar and petroleum solvents.

11. A method of insolubilzing and solidifying higher fatty acid esters of polyhydric alcohols characterized by their solubility in coal tar and petroleum solvents, which comprises treating said 20 esters with at least about 4.5 percent by Weight of an organic peroxide at a temperature of at least about C., and sufficiently elevated to effect substantially immediate and complete release of free oxygen therein to form a solidified reaction product in the form of a mass of incoherent, solid particles, said reaction product being insoluble in coal tar and petroleum solvents.

12. The method set forth in claim 10 wherein the higher fatty acid ester of the monohydric alcohol is an ester-wax.

13. The method set forth in claim 10 wherein the monohydric alcohol is a high atomic alcohol.

14. The method set forth in claim 11 wherein the polyhydric alcohol is a glycol.

15. The method set forth in claim l1 wherein the polyhydric alcohol is a glycerol.

16. The method set forth in claim 1 wherein the higher fatty acid ester of an alcohol comprises a resin.

17. The method set forth in claim 1 wherein the higher fatty acid ester of an alcohol comprises a wax.

18. The method set forth in claim 1 wherein the higher fatty acid ester of an alcohol comprises an oil.

19. The method set forth in claim 1 wherein the higher fatty acid ester of an alcohol comprises a resinous fatty acid polyhydric alcohol ester of a condensation polymer of epichlorohydrin and bisphenol.

MAX KRONSTEIN.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,811,078 Dykstra 4.--- June 23, 1931 1,975,959 Lawson Oct. 9, 1934 2,399,697 Stark May 7, 1946 2,403,408 Stamberger July 2, 1946 2,442,330 Fuller June 1, 1948 

1. A METHOD OF INSOLUBILIZING AND SOLIDIFYING HIGHER FATTY ACID ESTERS OF ALCOHOLS CHARACTERIZED BY THEIR SOLUBILITY IN COAL TAR AND PETROLEUM SOLVENTS, WHICH COMPRISES TREATING SAID ESTERS WITH AT LEAST ABOUT 4.5 PERCENT BY WEIGHT OF AN ORGANIC PEROXIDE, AT A TEMPERATURE OF AT LEAST ABOUT 90* C., AND SUFFICIENTLY ELEVATED TO EFFECT SUBSTANTIALLY IMMEDIATE AND COMPLETE RELEASE OF FREE OXYGEN THEREIN TO FORM A SOLIFIED REACTION PRODUCT IN THE FORM OF A MASS OF INCOHERENT, SOLID PARTICLES, SAID REACTION PRODUCT BEING INSOLUBLE IN COAL TAR AND PETROLEUM SOLVENTS. 